Sulfonated block copolymers, method for making same, and various uses for such block copolymers
View Patent ↗The present invention is a, solid block copolymer comprising at least two polymer end blocks A and at least one polymer interior block B wherein each A block is a polymer block resistant to sulfonation and each B block is a polymer block susceptible to sulfonation, and wherein said A and B blocks do not contain any significant levels of olefinic unsaturation. Preferably, each A block comprising one or more segments selected from polymerized (i) para-substituted styrene monomers, (ii) ethylene, (iii) alpha olefins of 3 to 18 carbon atoms; (iv) hydrogenated 1,3-cyclodiene monomers, (v) hydrogenated monomers of conjugated dienes having a vinyl content less than 35 mol percent prior to hydrogenation, (vi) acrylic esters, (vii) methacrylic esters, and (viii) mixtures thereof; and each B block comprising segments of one or more polymerized vinyl aromatic monomers selected from (i) unsubstituted styrene monomers, (ii) ortho-substituted styrene monomers, (iii) meta-substituted styrene monomers, (iv) alpha-methylstyrene, (v) 1,1-diphenylethylene, (vi) 1,2-diphenylethylene and (vii) mixtures thereof. Also claimed are processes for making such block copolymers, and the various end uses and applications for such block copolymers.
1. A sulfonated block copolymer which is solid in water comprising at least two polymer end blocks A, at least one polymer interior block B, and at least one polymer block D, wherein:
a. each A block and each D block is a polymer block resistant to sulfonation and each B block is a polymer block susceptible to sulfonation, said A and B blocks containing no significant levels of olefinic unsaturation;
b. each A block independently having a number average molecular weight between 1,000 and 60,000 and each B block independently having a number average molecular weight between 10,000 and 300,000;
c. each A block is a segment of one or more polymerized para-substituted styrene monomers;
d. each B block comprising segments of one or more vinyl aromatic monomers selected from polymerized (i) unsubstituted styrene monomers, (ii) ortho-substituted styrene monomers, (iii) meta-substituted styrene monomers, (iv) alpha-methylstyrene, (v) 1,1-diphenylethylene, (vi) 1,2-diphenylethylene and (vii) mixtures thereof;
e. said B blocks are sulfonated to the extent of 10 to 100 mol percent, based on the units of vinyl aromatic monomer in said B blocks;
f. the mol percent of vinyl aromatic monomers which are unsubstituted styrene monomers, ortho-substituted styrene monomers, meta-substituted styrene monomers, alpha-methylstyrene, 1,1-diphenylethylene and 1,2-diphenylethylene in each B block being between 10 mol percent and 100 mol percent;
g. said sulfonated block copolymer is non-dispersible and solid in water, and has a tensile strength greater than 100 psi in the presence of water according to ASTM D412 after immersion in water for 24 hours; and
h. each D block having a glass transition temperature of less than 20° C. and a number average molecular weight of between 1,000 and 50,000.
2. The sulfonated block copolymer according to claim 1 , wherein the polymer in said A block further comprises up to 15 mol percent of polymerized monomers selected from (i) unsubstituted styrene monomers, (ii) ortho-substituted styrene monomers, (iii) meta-substituted styrene monomers, (iv) alpha-methylstyrene, (v) 1,1-diphenylethylene, (vi) 1,2-diphenylethylene and (vii) mixtures thereof.
3. The sulfonated block copolymer according to claim 1 , wherein said A block is a segment of one or more polymerized para-substituted styrene monomers selected from para-methylstyrene, para-ethylstyrene, para-n-propylstyrene, para-iso-propylstyrene, para-n-butylstyrene, para-sec-butylstyrene, para-iso-butylstyrene, para-t-butylstyrene, isomers of para-decylstyrene, and isomers of para-dodecylstyrene.
4. The sulfonated block copolymer according to claim 1 , wherein said A block is a polymerized segment of para-t-butylstyrene and said B block is a polymerized segment of unsubstituted styrene.
5. The sulfonated block copolymer according to claim 1 , wherein said A block is a polymerized segment of para-methylstyrene and said B block is a polymerized segment of unsubstituted styrene.
6. The sulfonated block copolymer according to claim 1 , having the general configuration A-D-B-D-A, A-B-D-B-A, (A-D-B)nX, (A-B-D)nX, and mixtures thereof, where n is an integer from 2 to about 30, and X is coupling agent residue.
7. The sulfonated block copolymer according to claim 6 , wherein said B blocks are sulfonated to the extent of 20 to 90 mol percent, based on the units of vinyl aromatic monomer in said B blocks.
8. The sulfonated block copolymer according to claim 1 , wherein the mol percent of hydrophobic monomers in said block copolymers is sufficient for the block copolymer to be solid in water.
9. The sulfonated block copolymer according to claim 1 , wherein the mol percent of the end blocks is greater than 15%.
10. The sulfonated block copolymer according to claim 9 , wherein the mol percent of the end blocks is greater than 20%.
11. The sulfonated block copolymer according to claim 1 , wherein the interior block B is a hydrogenated copolymer of one or more unsubstituted styrene monomers, and monomers of conjugated dienes having a vinyl content of 20 to 80 mol percent prior to hydrogenation.
12. The sulfonated block copolymer according to claim 1 , having a water permeability greater than 0.1 times 10 −6 grams per Pascal.meter.hour, according to ASTM E96-00 “desiccant” method, a wet tensile strength greater than 500 psi according to ASTM D412, and a swellability of less than 100% weight after immersion in water for 24 hours.
13. The sulfonated block copolymer according to claim 12 , having a water permeability greater than 1.0 times 10 −6 grams per Pascal.meter.hour, according to ASTM E96-00 “desiccant” method and a wet tensile strength greater than 1000 psi according to ASTM D412 after immersion in water for 24 hours.
14. The sulfonated block copolymer according to claim 1 , having a ratio of wet tensile strength to dry tensile strength greater than 0.3.
15. The sulfonated block copolymer according to claim 1 , wherein at least about 20 mol percent of the monomers in the interior blocks B are sulfonated.
16. A sulfonated block copolymer which is solid in water after immersion in water for 24 hours and having the general configuration A-D-B-D-A, A-B-D-B-A, (A-D-B)nX, (A-B-D)nX, or mixtures thereof where n is an integer from 2 to about 30, and X is coupling agent residue wherein:
a. each A block and each D block is a polymer block resistant to sulfonation and each B block is a polymer block susceptible to sulfonation, said A, B and D blocks containing no significant levels of olefinic unsaturation;
b. each A block independently having a number average molecular weight between 1,000 and 60,000 and each B block independently having a number average molecular weight between 10,000 and 300,000;
c. each A block is a segment of one or more polymerized para-substituted styrene monomers;
d. each B block comprising segments of one or more vinyl aromatic monomers selected from polymerized (i) unsubstituted styrene monomers, (ii) ortho-substituted styrene monomers, (iii) meta-substituted styrene monomers, (iv) alpha-methylstyrene, (v) 1,1-diphenylethylene, (vi) 1,2-diphenylethylene and (vii) mixtures thereof;
e. each D block comprises polymers having a glass transition temperature less than 20° C. and a number average molecular weight of between 1,000 and 50,000, said D block being selected from the group consisting of (i) a polymerized or copolymerized conjugated diene selected from isoprene, 1,3-butadiene having a vinyl content prior to hydrogenation of between 20 and 80 mol percent, (ii) a polymerized acrylate monomer, (iii) a silicon polymer, (iv) polymerized isobutylene and (v) mixtures thereof, wherein any segments containing polymerized 1,3-butadiene or isoprene are subsequently hydrogenated;
f. said B blocks are sulfonated to the extent of 10 to 100 mol percent, based on the units of vinyl aromatic monomer in said B blocks;
g. the mol percent of vinyl aromatic monomers which are unsubstituted styrene monomers, ortho-substituted styrene monomers, meta-substituted styrene monomers, alpha-methylstyrene, 1,1-diphenylethylene and 1,2-diphenylethylene in each B block being between 10 mol percent and 100 mol percent; and
h. wherein said sulfonated block copolymer is non-dispersible and solid in water, and has a tensile strength greater than 100 psi in the presence of water according to ASTM D412 after immersion in water for 24 hours.
17. The sulfonated block copolymer according to claim 16 , wherein said A block is a polymer block of para-t-butylstyrene and said B block is a polymer block of unsubstituted styrene.
18. The sulfonated block copolymer according to claim 16 , wherein said A block is a polymer block of para-methylstyrene and said B block is a polymer block of unsubstituted styrene.
19. The sulfonated block copolymer according to claim 18 , wherein said D block prior to hydrogenation is polymer block of 1,3-butadiene, and wherein 20 to 80 mol percent of the condensed butadiene units in block D have 1,2-configuration prior to hydrogenation.
20. A sulfonated block copolymer which is solid in water comprising at least two polymer end blocks A, at least one polymer interior block B, and at least one polymer block D, wherein:
a. each A block and each D block is a polymer block resistant to sulfonation and each B block is a polymer block susceptible to sulfonation, said A and B blocks containing no significant levels of olefinic unsaturation;
b. each A block is a segment of one or more polymerized para-substituted styrene monomers, and each A block independently having a number average molecular weight between 1,000 and 60,000 and each B block independently having a number average molecular weight between 10,000 and 300,000;
c. said B blocks are sulfonated to the extent of 10 to 100 mol percent; and
d. wherein said block copolymer is neither water soluble nor water dispersible, and is solid and has a tensile strength greater than 100 psi in the presence of water according to ASTM D412 after immersion in water for 24 hours; and
e. each D block having a glass transition temperature of less than 20° C., said D block comprising a hydrogenated polymer or copolymer of a conjugated diene selected from isoprene, 1,3-butadiene having a vinyl content prior to hydrogenation of between 20 and 80 mol percent, and mixtures thereof, and having a number average molecular weight of between 1,000 and 50,000.
21. The sulfonated block copolymer of claim 20 , wherein said B block comprises a copolymer of unsubstituted styrene and isobutylene.
22. A sulfonated block copolymer which is solid in water at least two polymer end blocks A, at least one polymer interior block B, and at least one polymer block D wherein:
a. each A block is a segment of one or more polymerized para-substituted styrene monomers, and each A block and each D block is a polymer block resistant to sulfonation and each B block is a polymer block susceptible to sulfonation, said A and B blocks containing no significant levels of olefinic unsaturation;
b. each A block independently having a number average molecular weight between 1,000 and 60,000 and each B block independently having a number average molecular weight between 10,000 and 300,000;
c. said B blocks are sulfonated to the extent of 10 to 100 mol percent; and
d. wherein said block copolymer is neither water soluble nor water dispersible, and is a solid, and has a tensile strength greater than 100 psi in the presence of water according to ASTM D412 after immersion in water for 24 hours; and
e. said D blocks having a glass transition temperature of less than 20° C., said D block comprising a polymer block of polymerized isobutylene, a polymerized ether, a polymer of an acrylic ester or a silicon polymer having a number average molecular weight of between 1000 and 50,000.
23. An article formed at least in part from a composition comprising the sulfonated block copolymer of claim 1 , said article being selected from the group consisting of fuel cells, fabrics, coated fabrics, membranes, filtration membranes, desalination membranes, air conditioning membranes, heat recovery membranes, coatings for membranes, personal hygiene articles, adhesives, hydrogels, antifouling coatings, water absorption articles, electrode assemblies, and marine coatings.
24. A composition comprising the sulfonated block copolymer of claim 1 and additional components selected from the group consisting of pigments, antioxidants, stabilizers, surfactants, waxes, flow promoters, particulates, fillers, and oils.
25. A composition comprising the sulfonated block copolymer of claim 1 and additional components selected from the group consisting of other polymers, polymer liquids and fillers.
26. The composition according to claim 25 , wherein the other polymers are selected from the group consisting of olefin polymers, styrene polymers, tackifying resins, hydrophilic polymers and engineering thermoplastic polymers.
27. The composition according to claim 26 , wherein said styrene polymers are selected from crystal polystyrene, high impact polystyrene, medium impact polystyrene, syndiotactic polystyrene, sulfonated polystyrene, styrene/acrylonitrile/butadiene polymers and styrene/olefin copolymers.